Process of treating waste sulfite liquor and compound obtained therefrom.



Uh i;

HENRY HICKS HURT, 0F COVINGTQN, VIRGINIA, ASSIGNQR T0 JACQB S. ROBESJGN, 0F

EROCE$$ 0F TREATING WASTE SULFXTE Ll No Drawing.

AU SABLE FURKS, NEW YQRZK.

QUOR AND COMPOUND OBTAINED THERLEFZRGM.

Application filed February 2951908.

Specification of Letters LPatent.

.ll atented Ml, was.

Serial No. 418,513.

To all whom [If may comxc'rn:

3e it known that I, Hnnnr a citizen of l-licns lluirr, the United States, and a resident of Covington, rilleghany county, Virginia,

pound Obtained 'lheret'rom,

invented an Improved Process of Liquor and Cornof which the Vaste Sulfite following is a specification.

My inve matter and ntion relates to compositions of the method of making the same;

and it comprises a composition containlng a compound changed organic m of a sesquioxid base with unatters of waste sulfite liquor and'the process of preparing the same.

My improved process comprises the treatment of waste sultitehquor, which may he in a warm ural components ch anged st but should contain its natin a substantially .1111- 1th a soluble salt of a sesstate,

ate, w

quioxid with an acid capable of forming insoluble salts w ith the base or bases contained in such sulfite liquor by the separation of such insoluble salt, and the subsecompound of the ganic matt l have discovered that uor eo-ntaimng its natural organic sultite liq matters in ent purification of the soa substantially unchanged state with certain reagents to produce a combination therein with a sesquio such organic matters existing Xld base. 1 can produce new compounds of great utility in the arts, such compounds for instance being suscepl ible of use in tanning and mordanting,

besides forming adhesives of a highly desirable nature.

in the manufacture of cellulose or paper pul process,

lime, a known as that hither ing highly ways and very difiicult of d atent granted to Jacob S.

ing such w i-overil'ig' the gre matter. as ins, gums under What is know which consists in boiling W other fibers under pressure n a solution containing sulfurous acid large quantity of a waste sultite liquor sulfite cod and n as the and a base, such as watery mixture is produced, to has had little value besides beobjectionable in a niunber of is )osal. In the Itobeson. Octoaste liqum'i'or. the purpose of reater portion of the colloidal well as all of the contained resand other extracted constituents l l l l of the woody tissue, is fully described and claimed, and for carrying out the process forming the subject of my intention, ll prefer to use a concentrated body of the material made in accordance with the patented process. 'lhis material ontains the natural organic matters of the sultite liquor in a substantially unchanged state. It will be understood, however, that my improved process can be carried into operation with the thin liquor as received from the digester, or at any degree of concentration short of dryness; the liquor being further concentrated, if desired, to any degree, after treatment according to my process.

Waste liquors from the digestion of spruce wood, (licca aloe), such for instance as those treated in accordance with the patented process, appear to have organic constituents particularly applicable to the present purpose, although similar liquors from the digestion of other woods may be employed. The waste liquor when concentrated in accordance with the patented process appears to have itsOrganic matter in substantially the same condition as in the original 1i nor; retaining to the full the original, p ysical and chemical characteristics of such matter. This I believe to be, essential for the present pur ioses. since with such organic matter altered or changed in any way, compositions are produced which are of much less value.

On boiling wood with solution of acid sulfites, such as calcium acid sulfite, in the well-known sultite process of making paper pulpfa large percentage of the wood 'oes into solution, forming new compounds with the sulfite, these compounds probably, at least to a large extent, being in the nature of salts of a sulfonic acid; the dissolved organic matter uniting with the acid radical to form new organic compounds of the nature of sulfonic acids and these newcompounds forming sulfonates with the base present. in boiling down the sulfite liquor by the process described and claimed in the stated patent, these organic matters of the original sulfite liquor remain substantially unchanged; that is, the concentrated product contains the same sultonates and other bodies that exist in the original sulfite liqnor.

'As the sulfite liquor usually contains lllllu ably free from lime and preference,

as a base neutralizing the organic and sulfonated organic matters present, composi tions under the present invention can be simply and easily made by mixing such sulfite liquor, preferably as stated in the concentrated form, with a solution of a sulfate of a sesquioxid. Other sesquioxid salts may be employed, but the sulfates are cheap and are highly convenient and satisfactory for this purpose. lime present in the sulfite liquor to form in soluble sulfate of calcium, which separates out and leaves in solution the organic matter of the sultite liquor combined with the sesquioxid base employed.

As the sesquioxid, I may employ ferric oxid, aluminum or chromium oxid; depending upon the particular purpose to which the resulting composition is to be applied. In using a sulfate of a sesquioxid, I may use either the simple sulfate, such as ferric sulfate, aluminum sulfate or chromium sulfate. or I may use the corresponding alums. For most purposes; however, the latter are less advantageous, as they leave the solution encumbered with salts.

in carrying my improved process into operation, I proceed substantially as fol lows: To about two hundred (200) pounds of the concentrateddiquor made in accordauce with the patented process, at a consistency of about 31 B., (or proportionate amounts, relative to the degree of concen- .tration,) and at a suitable temperature, I

add from twenty (20) to twenty-five (25) pounds of ordinary sulfate of alumina of commence. The sulfate of alumina may be dissolved prior to its admixture With the waste sulfite liquor in from forty (40) to seventy-five (75) pounds of water prefermagnesia, and, by distilled water. Where iron or' chromium compounds are desired, proportional amounts of ferric or chromic sulfate may be substituted for the aluminum sulfate. The temperature at which this reaction is performed is not a matter of indifference. When the solutions of the sesquioxid salt and the concentrated waste or less flocculent, filters well,

liquor aremixed in the cold, the precipitate takes a greater time to form. It is better, therefore, to perform this precipitation with the liquids warm, the more so as such action gives a precipitate of better physical character, indicative of a more complete removal of the lime salts and other When the concentrated process by evaporating such liquor in a multiple effect, concentrated liquid. leaves the last efi'ect is a convenient one; this temperature generally being around 130 to 140 F. The precipitate made under these conditions is more and is capable Such sulfates react with the the temperature at which the second precipitate, which appears to be mainly free sulfur.

This sulfur is probably derived from the original waste sultite liquor, in which it may be in solution, or

pseudosolution, or perhaps in the form of a salt of one of the thionic acids. ever the form in which the sulfur exists in the original liquor, in which form it is apparently tolerably permanent, yet when the organic matters combine with the sesquioxid base as'described, it becomes in soluble and settles Out. For some of the uses, as for instance, in tanning, for which my improved compositions are available this sulfur may be removed, and as stated, it settles out after the liquid stands for some time and may then be filtered 0%, or the liquid decanted away.- After the sec-. ond purification, the liquid may be brought to any desired density, as by evaporation and condensation or by dilution with water.

The contained compound of a sesquioxid base with the organic matters existing in waste sulfite liquor, appears to be quite stable in character, allowlng such compound to be transported and stored without substantial change occurring, other than the stated separation of sulfur. Upon isolating this compound from the substantially pure solution formed as described, as by evaporating such solution to dryness, it is. found to be perfectly soluble hibiting no tendency to set or become insoluble. For many purposes it may be desirable to reduce the compound produced according to the prescribed method to dryness, since solutions of the same may be readily produced by addition of water to such solid matter, the solutions so prepared having substantially the properties of the original solution;

The compositions or compounds produced in the described manner are susceptible of many uses. That formed by the addition of aluminum sulfate to the waste liquor is an excellent tanning agent and in acompanion application filed February 29, 1908, Serial No. 418,514, I have described a process of tanning in which such material is employed; the chromium compound is also applicable for this purpose; the iron compound is not so well'suited for tanning, but is susceptible of use as an adhesive in the briqueting of finely divided material and for other purposes of a similar nature. The aluminum compound is also capable of serving as an adhesive and sizing material; both of the constituents beingsoluble in alkali, it may be mixed with or dissolved in alkaline sizing material, such as rosin size, although the aluminum compound is believed llVhatto be a good sizing material per se. The iron compound, because of its cheapness, may well be used for many purposes. 1n

tanning, the aluminum and chromium compounds are particularly advantageous.

T claim:

1. As a new composition of matter, a composition containing a compound of a sesquioxid base with the organic matters of sultite waste liquor said composition containing the organic matters of sultite waste liquor in substantially their original relative ratios and of substantially their origin-ll composition.

2. As a new composition of matter; a compound of alumina with the organic matters of waste sulfite liquor, said composition containing the organic matters of sulfite waste liquor in substantially their original relative ratios and of substantially their original composition.

3. its a new composition of matter, a solution containing the organic matters of suliite waste liquor; in substantially their original relative ratios and of substantially their original composition, said solution being substantially freeof lime and containing a dissolved sesquioxid base in the amount equivalent to the lime of unchanged sulfite liquor.

4. As a new composition of matter, a solution containing the organic matters of sul tit-e waste liquor in substantially their original relative ratios and of substantially their original composition, said 'solutionbeing substantially free of lime and containing alumina in the amount equivalent to the lime of unchanged sulfite liquor.

5. The process of making a tanning conipositionwhich comprises reacting upon a sulfite waste liquor preparation containing the original organic matters in their normal relative ratio and of their normal character with a salt of a sesquioxid with an acid able to form insoluble lime salts, and removing the insoluble lime salt produced.

6. The process of making a tanning comwith a salt of alumina with an acid able to form insoluble lime salts, and removing the insoluble lime salt produced.

7. The process of making a tanning composition which comprises reacting upon a sulfite waste liquor preparation containing the original organic matters in their normal relative ratio and of their normal character with a sulfate of a sesquioxid, and removing the insoluble calcium sulfate formed.

8. The process of making a tanning composition which comprises reacting upon a sulfite waste liquor preparation containing the original organic matters in their normal relative ratio and of their normal character with a sulfate of alumina, and removing the insoluble calcium sulfate formed.

9. Theprocess of making a tanning composition which comprises reacting upon a sulfite waste liquor preparation containing the original organic matters in their normal relative ratio and of their normal character with a sulfate of a sesquioxid, removing the insoluble calcium sulfate formed and removing the' free sulfur subsequently pre-' cipitated.

10. The process of making a tanning composition which comprises reacting upon a sulfite waste liquor preparation containing the original organic matters in their normal relative ratio and of their normal character with a sulfate of alumina, removing the insoluble calcium sulfate formed and removing the free sulfur subsequently precipitated.

In testimony whereof, IV have signed my name to this specification, in the presence of two subscribing witnesses.

HENRY HICKS HURT.

Witnesses WILLIAM Anne, L. H. Gno'rn. 

